Protective and decorative coating



Patented June 27, 1944 rao'rnc'rrvc AND DECORATIVE" coArmG Lazld Auer,East Orange, N. 1., assignor to Ridbo Laboratories, Inc., Paterson, N.J., a corporation ofNew Jersey No Drawing. Application November 25,1941,

Serial No. 420,346

11 Claims.

newcomposition being particularly suitable for relatively inexpensivepaints such as one-coat interior architectural paints, for exampleglosspaints and flat wall paints.

The drying oils, for instance linseed oil, commonlyused in certainclasses of paints are relatively expensive, in view of which, forinexpensive paints, it has been common to substitute the less expensivesemi-drying oils, for example soya bean oil, fish oils (menhaden orsardine oils), in place of the more expensive drying oils, such aslinseed oil. I Whether such paints (containing semi-drying oils, orother substitutes for drying oils) are applied in one or more coats, andespecially where eifective coverage is expected from a single coat, thequality of the protective coating is impaired in certain respects (ascompared with paints containing high quality drying oils), and notablyin the respect discussed just below. The reason why especial difficultyis encountered where eifective coverage is expected from a single coatis that "one-coat work requires application of a thicker layer thanwhere several coats are used, and one thick coat dries on and throughmore slowly and less completely.

It is found that at least certain components of the semi-dryingingredient sweat out," usually subsequently to the initial drying,producing a sticky surface, probab1y due to synaeresis. This effect ismore pronounced when the paint is appiled on a humid or "bad drying"day. Even if the atmospheric conditions at the time of application ofthe coating are ideal for drying and apparently produce good initialdrying, re-liquefying andvsweating out of components of the dryingingredient will frequently take place as long as several months or morefollowing application of the coating, this effect usually beingmanifested in a period of hotand/or humid weather.

I have found that a good quality inexpensive paint, highly effective andsatisfactory even for one-coat work, may be made by replacing the oil isused conjointly with said ro'sin-terpene hydrocarbon mixture, thetendency for the semidrying oil to re-liquefy and sweat out is virtuallycompletely eliminated. (What I herein refer to as a rosin-terpenehydrocarbon mixture will be brought out more fully hereinafter.)

Moreover, the employmentof a rosin-terpene hydrocarbon mixture, as adrying ingredient, im

parts to the paint other desirable characteristics,

including high wetting power, and quick top-dry ing coupled with goodthroughdrying.

When properly formulated, the topand through-drying characteristics of apaint in accordance with this invention are such that the paint mayeffectively be used for one-coat work without surface wrinkling and withexcellent through-drying, even where a heavy layer is applied, as isnecessary for complete coverage in one coat.

With respect to the matter of cost of ingreclients, it is noted that aneconomic gain results not only from use of the rosin-terpene hydrocarbonmixture in substitution for oils, but also from the fact that at leastsome semi-drying oils of lower quality than has been practicable to useheretofore may be employed in combination with the rosin-terpenehydrocarbon mixture, since the re-liquefying which is most noticeablewith the lower quality semi-drying oils is reduced or eliminated byvirtue of their conjoint use with the rosin-terepenehydrocarbon'mixture.

Where the rosin-terpene hydrocarbon mixture is used in combination withsemi-drying oils, the latter may satisfactorily be employed in amountsranging from about 100% to about 101% of the of the quantity ofrosin-terpene hydrocarbon mixture. A ratio of about one part ofsemi-drying oil to four parts of said mixture has been found'acteristics normally expected from the resinous istics'oi both, andtherefore cannot be substituted pou'nd-fon-pound for resin or oil inexisting paint formulas. i

In addition to advantages already noted, it may be mentioned that therosin-terpene hydrocarbon mixture cuts very rapidly with solvents andoils, which is frequently of importance not only in initial preparationof the paint, but also in any subsequent cutting which may be desired. 7

In accordance. with the preferred practice of.

the invention, the rosin-terpene hydrocarbon,

mixture-is prepared preliminarily and. thereafter introduced as suchinto the paint mix.

Several methods for initially. providing the rosin-terpene hydrocarbonmixture are briefly described hereinafter. It .is first noted, however."that both the rosin and terpene components are preferably derived fromnatural rosins such as'gu'm and wood 'rosins.

Inthe preferred practice of the invention, the

amongst others.

rosin is heated to a temperature between, about having an initialacid-value of 160, the treatment is preferably. carried out to reducethe acid value to a point lying between about 120 and 20. This rangegives, a mixture varying from about,75% to 12.5% rosin and from about25% to 87.5% terpene hydrocarbons.

The treatment specifically referred to above gives an acid value ofabout 60-80 and, for many purposes, I have found that a desirable acidvalue range corresponds roughly to a' 50-50 ratio between rosin andterpene hydrocarbons, i. e., an acid value between '10 and 85.

The treatment described above not only effects partial decar'boxylationbut, in addition. other changes are brought about, apparently because ofcolloidal transformations in the rosin (which I believe to be anisocolloid), in consequence of which the rosin is softened or liquefied.Rosin treated in accordancewith the foregoing and having an acid numberbetween about 60 or 70 and about 85- comprises a plastic or soft solidmass, with a cold flow. It further has high wetting power andgood topandthrough-drying characteristics.

-.'I'he treatment to produce the rosin-terpene hydrocarbon mixture maybe varied in a number of respects, .as disclosed, for example, in mycope'nding application Serial No. 386,371, filed April 1-, 1941 (PatentNo; 2,311,200, February 16, 1943) of which the present application is acontinuation-in-part, ,and also disclosedin my prior applications'Serial Nos. 318,650, filed February 12, 1940 (Patent "No. 2,298,270,October 13, 1942); 446,171, filed April 21, 1930 (Patent 1,980,367,

November 13, 1934); 359,425, filed April 30, 1929 (Patent 2,213,944,September 10, 1940); and 143,- 786, filed October 23, 1926 (Patent2,189,772, February 13; 1940): all of which prior applications disclosesimilar treatment of rosin. I

For the present purposes,'I-prefer to use zinc terpene hydrocarbonmixture.

carbonate .(as disclosed in said application 386,-

371) as'a'modifying agent in preparation of the iosimlalthough otheragentsmay be employed es such as zinc chloride and agents disclosed invariour of my earlier applications, for instance magnesium suiphate andammonium iodide. as inen-' tioned in application 380,371,, and p-toluenesulphonic acid-and p-toluene sulphochloride, as 'mentionedin myPatent1,980,367. The quantity of modifying agent employed may be from anappreciable trace (fractional percentage) to about 30%, and preferablyfrcmia trace to about 10%.,

'od for producing the "rosin-terpene hydrocarbon mixture clarifies whatI mean by that expression. In further explanat on of this useof theterms rosin and terpen hydrocarbons," it may be stated that by "rosin Imean commercial gumlrosin and/or wood rosin products, containingmixtures of rosin acids, known today as abietic acid, pyroabietic acidand d-pimaric acid, By terpene hydrocarbons I mean terpene radicals ofrosin acids, such as abietene, or high molecular. residues of suchterpene radicals of rosin'acids. By the term "residue, used just above,I mean either the terpene molecule secured by a secondary splitting oil?of radicals (secondary to the. primary decarboxylation), for instance,methyl groups, etc.'; or the terpene molecule-after changes inunsaturation (hydrogen content) of the original molecule; such,

products being obtairieddrom rosin acids in the course of the treatmentused toprepare the rosin- It may be mentioned that typical rosinscontain about abietic acid.

Although my preferred method-for producing the mixture also brings.about other changes in therosin undentreatment, the rosin-terpenehydrocarbon mixture consists essentially dr in major part of abieticacid and abietene in the ratios hereinbefore referred tor A similarmixture of the same essential or In accordance with another method forpro- I ducing rosin oil, rosin is heated at from 150 C'. to 325 C.(preferably at about 300 C.), with 2% of a siliceous earth or ofactivated carbon.

Rosinoil produced in accordance with the foregoing or other knownmethods may be remixed with rosin in the desired proportions, in orderto produce the rosin-terpene hydrocarbon mixture herein contemplated. g.

Although I prefer a) preliminarily prepare the rosin-terpene hydrocarbonmixture and then add said mixture as such to the paint mix, it is to beunderstood that the two components of the mixture may be added'to thepaint mix individually under some circumstances.

Exmrs 1 An example of a fiat wall paint prepared in accordance with thisinvention is as follows:.

Grinding mixture Pounds Ti-Cal-(titanium-calcium pigment) 450 JIiO: ISurfex (surface treated calcium carbonate) 400 Asbestine .Q, 100

; Alkali'refined soya beanoil 60 Rosin-terpene hydrocarbon mixtureKerosene After rough grinding of the foregoing mixture the remainder ofthe vehicle was added:

Reduction Pounds 1% soap solution l2 Blown soya bean oil Mineral spirits71 8% strong zinc drier 2 24% strong lead drier d A second rough grindfollowed.

Instead of the soya bean oil referred to in the above example, fish oilsor heat-bodied linseed oil may be used.

EXAMPLE 2 An example of one-coat gloss paint is as follows:

Pounds 'Ii-Cal (titanium-calcium pigment) 180 TiOa Suriex (surfacetreated calcium carbonate) -4. 200 Rosin-terpene hydrocarbon mixture266.7 Alkali refined soya bean oil 133.3 I Mineral spirits 60 vantageousin Example 2 to use zinc or calcium driers, to enhance through-drying.In calculating, the proper drier proportions, the rosinterpenehydrocarbon mixture should be regarded as oil content, since it requiresdriers for proper film formation.

In Example 2, the soya bean oil may be replaced with a substantially.equal amount either of heavy-bodied linseed oil, or of processed fishoil (for instance, a fish oil treated with ester gum and containingabout 85% solids and 15% mineral spirits), With such substitutions somevariation in the quantity of mineral spirits might be desirable.

In addition to the two examples above, others were prepared generallyfollowing certain known paint formulas. Thus- E'xample 3 47%titanium-calcium pigment,

rutile 54% pigment" 53% precipitated calcium' car- I bonate 74% solids(limed rosin, varnish linseed:oil, ester-gum treated fish oil (85%solids and 15% mineral spirits)) 26% volatile etc.)

gallons) If in the foregoing formula, all of the linseed oil and part ofthe limed rosin are replaced by the rosin-terpene hydrocarbon mixture,to the extent of 68% of the vehicle solids, the paint has the followingcharacteristics:

Body of paint.I-Ieavier than Standard Flow.-More flow than Standard butno sa s s 46% vehicle (mineral spirits,

(oil length' about '11 Brushing propertiea- -Slightly easier workingthan Standard- Glosa-Better gloss than Standard Gloss retention-Betterthan Standard Drying.-Good 1 Hardness overnight-Equal to Standard Skinformation-No skin in 48 hours Settling.-In 30 days equal to Standard Ifin the above iormula the ester gum treated fish oil and a part of thelimed rosin be replaced with the rosin-terpene hydrocarbon mixture tothe extent of 58% of the non-volatile of the vehicle, thecharacteristics are very similar to those of the paint in which thelinseed oil and part of the limed rosin are replaced by therosin-terpene hydrocarbon mixture. It may be noted, how-' ever, that thepaint in which the fish oil is replaced and the linseed oil retained hasbetter brushing properties than the paint containing no linseed oil.

ExAmLn 4 A known fiat white wall paint formula is as follows:

76% rutile, titanium calcium pig- 67% pigment--- precipitated calciumca'rbonate 38% solids (limed rosin, linseed oil and dehydrated castoroil) 33% vehwle" 62% volatile-mineral spirits, etc.

(oil length about 182' gallons) In the above formula the rosin,dehydrated.

castor oil and part 0! the linseed oil were replaced with therosin-terpene hydrocarbon mixture, to the extent of 64% of the vehiclesolids. With this substitution, the paint was characterized as followerBody of point-Heavier than Standard Flow-Equal to Standard Brushing pr prties-Harder working Standard Drying.-Harder than Standard Skinformation.None observed Settling.--Fair Satisfactory paints were securedin both of Examples 3 and 4, at substantially reduced cost, and in allcases the paint was free, from re-liquefying of the drying ingredients.I

I claim: I

1. In a paint, a vehicle containing substantially non volatiie rosiningredients as at least than the major drying and film-formingconstituents.

said ingredients comprising treated rosin material prepared by heatingrosin to a decarboxylation temperature the presence, of a decalboigylation promoting agent to partially decarboxylate said rosin, and saidingredients further being characterized by the presence of both rosinacids and rosin hydrocarbons, and the rosin ingredients having an acidvalue of from 20 to 120, and said vehicle being characterized by a'highdegree of wetting power. good topand throughdrying characteristics, andsubstantial freedom from reliqueiying of the drying and film-formingingredients after formation of the paint film.

2. A composition in accordance with claim 1 in which the acid valueofthe rosin ingredients is between about 60 and so.

3, A composition in accordance with claim 1 and further incorporating asemi-drying fatty oil, the quantity or which is between 10% and of thecombined content oi rosin acids and rosin hydrocarbons.

4. A composition in accordance with claim l'in which the paint vehiclefurther incorporates a fatty oil in an amount less than the combinedquantity of rosin acids and rosin hydrocarbons present. a

5. A composition in accordance with claim 1 in'which the paint vehiclefurther incorporates a. semi-drying fatty oil in an amount less than thecombined quantity of rosin acids and rosin hydrocarbons present. I

6. A composition in accordance with claim 1 in which the paint vehiclefurther incorporatesflsh oil in anamount less than the combined quantityof rosin acids and rosin'hydrocarbons present.

7. A composition in accordance with claim 1 in which the paint vehiclefurther incorporates soya bean oil in an amount less than the combinedquantity of rosin acids and rosin hydrocarbons present.

. '20 8. A composition in accordance with claim 1 in tially non-volatilerosin ingredients as ,at least' the major drying and film-formingconstituents. said ingredientseomprising at least three main materialsincluding rosin acids, rosin hydrocarbons, and the reaction product ofrosin and zinc carbonate prepared by heating at a decarboxylationtemperature, and the rosin'ingredients having an acid value or from 20to I20, and said vehicle being characterized by a high degree. ofwetting power. good topand throughedrylng characteristics; andsubstantial freedom from reliquei'ying or the drying and film-formingingredien'ts after formation of the paint film.

11. In a. paint, a vehicle containing substanytially non-volatile rosiningredients as at least the major drying and film-forming constituents,saidingredients comprising treated rosin material preparedby-application of heat at a decarboxylation temperature in the presenceof a decar xylation promoting agent, and under conditions avoidingappreciable distillation, the rosin ingredients. including rosin acidsand rosin hydrocarbons, and said ingredients having an acid value-oifroin20 to 120, and said vehicle beingv characterized by a highdegree'oi' wetting power, good topand through-drying characteristics.

and substantial freedomirom reliquefylng or the drying and film-formingingredients after formation of the paint film.

- Anna.

